rac-Ethyl 4-hy-droxy-6-(2-hy-droxy-phen-yl)-2-oxo-4-(trifluoro-methyl)per-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C(14)H(15)F(3)N(2)O(5), prepared by reaction of 2-hy-droxy-benzaldehyde, ethyl 4,4,4-trifluoro-3-oxobutano-ate and urea, the tetra-pyrimidine ring adopts a half-chair conformation. The crystal structure is stabilized by five inter-molecular hydrogen bonds, three O-H⋯O and two N-H⋯O, giving cyclic dimers (through three hydrogen bonds) which are further extended into a two-dimensional network.

Related literature

For the bioactivity of dihydro­pyrimidines, see: Brier et al. (2004 ▶); Cochran et al. (2005 ▶); Moran et al. (2007 ▶); Zorkun et al. (2006 ▶). For the bioactivity of organofluorine compounds, see: Hermann et al. (2003 ▶); Ulrich (2004 ▶).

Experimental

Crystal data

C14H15F3N2O5

M = 348.28

Monoclinic,

a = 12.0940 (15) Å

b = 8.665 (1) Å

c = 14.3110 (18) Å

β = 93.987 (6)°

V = 1496.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 113 K

0.26 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn724 CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ▶) T min = 0.965, T max = 0.973

15222 measured reflections

3558 independent reflections

2461 reflections with I > 2σ(I)’

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.075

S = 0.96

3558 reflections

234 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CrystalClear-SM Expert (Rigaku, 2009 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2009 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810021355/zs2042sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021355/zs2042Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H15F3N2O5	F(000) = 720
Mr = 348.28	Dx = 1.546 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 4600 reflections
a = 12.0940 (15) Å	θ = 1.7–28.0°
b = 8.665 (1) Å	µ = 0.14 mm−1
c = 14.3110 (18) Å	T = 113 K
β = 93.987 (6)°	Prism, colorless
V = 1496.1 (3) Å3	0.26 × 0.22 × 0.20 mm
Z = 4

Rigaku Saturn724 CCD diffractometer	3558 independent reflections
Radiation source: rotating anode	2461 reflections with I > 2σ(I)'
multilayer	Rint = 0.043
Detector resolution: 14.222 pixels mm-1	θmax = 27.9°, θmin = 2.1°
ω scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −10→11
Tmin = 0.965, Tmax = 0.973	l = −18→15
15222 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ2(Fo2) + (0.0366P)2] where P = (Fo2 + 2Fc2)/3
3558 reflections	(Δ/σ)max < 0.001
234 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
F1	0.63046 (7)	0.13597 (8)	0.56068 (5)	0.0284 (2)
F2	0.70104 (6)	−0.07799 (8)	0.61474 (5)	0.02243 (19)
F3	0.52483 (6)	−0.04190 (9)	0.61064 (5)	0.0278 (2)
O1	0.73825 (7)	0.17971 (10)	0.73408 (6)	0.0166 (2)
O2	0.57743 (7)	−0.12700 (9)	0.92883 (6)	0.0155 (2)
O3	0.61021 (7)	0.46053 (9)	0.68641 (6)	0.0188 (2)
O4	0.44283 (7)	0.37553 (9)	0.63011 (6)	0.0189 (2)
O5	0.57096 (8)	0.57378 (10)	0.88466 (7)	0.0226 (2)
N1	0.62882 (9)	−0.02277 (12)	0.79262 (7)	0.0144 (2)
N2	0.52802 (9)	0.11947 (11)	0.89483 (8)	0.0151 (2)
C1	0.63604 (10)	0.10070 (14)	0.72522 (9)	0.0136 (3)
C2	0.54011 (10)	0.21315 (13)	0.73746 (8)	0.0128 (3)
H2	0.4693	0.1572	0.7201	0.015*
C3	0.53875 (10)	0.26147 (13)	0.84121 (8)	0.0139 (3)
H3	0.6103	0.3134	0.8614	0.017*
C4	0.57828 (10)	−0.01283 (14)	0.87496 (9)	0.0137 (3)
C5	0.62326 (10)	0.02811 (14)	0.62678 (9)	0.0169 (3)
C6	0.53918 (10)	0.36240 (14)	0.68090 (8)	0.0144 (3)
C7	0.41216 (11)	0.52976 (14)	0.59613 (10)	0.0219 (3)
H7A	0.4704	0.5723	0.5582	0.026*
H7B	0.4024	0.6003	0.6494	0.026*
C8	0.30531 (11)	0.51220 (17)	0.53746 (10)	0.0273 (3)
H8A	0.3166	0.4433	0.4847	0.033*
H8B	0.2806	0.6135	0.5137	0.033*
H8C	0.2489	0.4683	0.5757	0.033*
C9	0.44302 (10)	0.37055 (13)	0.85540 (8)	0.0145 (3)
C10	0.46361 (10)	0.52609 (14)	0.87614 (8)	0.0157 (3)
C11	0.37451 (11)	0.62576 (15)	0.88661 (9)	0.0203 (3)
H11	0.3882	0.7312	0.9014	0.024*
C12	0.26690 (11)	0.57248 (15)	0.87573 (9)	0.0233 (3)
H12	0.2071	0.6412	0.8836	0.028*
C13	0.24560 (12)	0.41890 (15)	0.85339 (10)	0.0248 (3)
H13	0.1715	0.3824	0.8452	0.030*
C14	0.33378 (11)	0.31964 (15)	0.84326 (9)	0.0204 (3)
H14	0.3194	0.2146	0.8277	0.024*
H1	0.7889 (15)	0.1108 (18)	0.7422 (12)	0.046 (5)*
H4	0.6684 (12)	−0.1011 (15)	0.7884 (9)	0.021 (4)*
H5	0.4973 (12)	0.1248 (15)	0.9477 (11)	0.025 (4)*
H6	0.5734 (13)	0.6771 (19)	0.8967 (11)	0.043 (5)*

	U11	U22	U33	U12	U13	U23
F1	0.0430 (5)	0.0269 (4)	0.0157 (4)	0.0048 (4)	0.0052 (4)	0.0046 (3)
F2	0.0214 (4)	0.0232 (4)	0.0232 (4)	0.0060 (3)	0.0047 (3)	−0.0049 (3)
F3	0.0180 (4)	0.0365 (5)	0.0285 (5)	−0.0054 (4)	−0.0001 (3)	−0.0131 (4)
O1	0.0097 (4)	0.0138 (5)	0.0264 (5)	−0.0005 (4)	0.0010 (4)	0.0003 (4)
O2	0.0196 (5)	0.0110 (4)	0.0161 (5)	0.0002 (4)	0.0029 (4)	0.0015 (4)
O3	0.0161 (5)	0.0168 (5)	0.0234 (5)	−0.0030 (4)	−0.0004 (4)	0.0028 (4)
O4	0.0151 (5)	0.0168 (5)	0.0241 (5)	0.0006 (4)	−0.0041 (4)	0.0051 (4)
O5	0.0165 (5)	0.0134 (5)	0.0381 (6)	−0.0009 (4)	0.0021 (4)	−0.0064 (4)
N1	0.0154 (5)	0.0115 (5)	0.0168 (6)	0.0045 (4)	0.0049 (4)	0.0010 (4)
N2	0.0197 (6)	0.0118 (5)	0.0146 (6)	0.0027 (4)	0.0065 (4)	0.0009 (4)
C1	0.0105 (6)	0.0133 (6)	0.0172 (7)	−0.0007 (5)	0.0014 (5)	0.0020 (5)
C2	0.0114 (6)	0.0120 (6)	0.0150 (7)	0.0009 (5)	0.0013 (5)	0.0010 (5)
C3	0.0135 (6)	0.0131 (6)	0.0152 (7)	0.0001 (5)	0.0017 (5)	0.0014 (5)
C4	0.0113 (6)	0.0132 (6)	0.0163 (7)	−0.0022 (5)	−0.0009 (5)	−0.0015 (5)
C5	0.0148 (6)	0.0171 (6)	0.0189 (7)	0.0016 (5)	0.0027 (5)	0.0010 (5)
C6	0.0128 (6)	0.0166 (7)	0.0138 (7)	0.0021 (5)	0.0020 (5)	−0.0009 (5)
C7	0.0209 (7)	0.0161 (7)	0.0282 (8)	0.0041 (5)	−0.0009 (6)	0.0072 (6)
C8	0.0217 (7)	0.0306 (8)	0.0291 (8)	0.0048 (6)	−0.0013 (6)	0.0094 (6)
C9	0.0148 (6)	0.0139 (6)	0.0153 (7)	0.0023 (5)	0.0036 (5)	0.0024 (5)
C10	0.0149 (6)	0.0150 (6)	0.0172 (7)	0.0009 (5)	0.0015 (5)	0.0004 (5)
C11	0.0209 (7)	0.0143 (7)	0.0257 (8)	0.0033 (5)	0.0018 (6)	−0.0028 (6)
C12	0.0178 (7)	0.0223 (7)	0.0302 (8)	0.0081 (6)	0.0045 (6)	−0.0003 (6)
C13	0.0150 (7)	0.0246 (7)	0.0353 (8)	0.0003 (6)	0.0049 (6)	−0.0016 (6)
C14	0.0183 (7)	0.0147 (7)	0.0289 (8)	−0.0005 (5)	0.0059 (6)	−0.0017 (6)

F1—C5	1.3370 (14)	C2—C3	1.5438 (17)
F2—C5	1.3350 (14)	C2—H2	1.0000
F3—C5	1.3418 (14)	C3—C9	1.5191 (16)
O1—C1	1.4110 (14)	C3—H3	1.0000
O1—H1	0.858 (17)	C7—C8	1.4990 (19)
O2—C4	1.2547 (14)	C7—H7A	0.9900
O3—C6	1.2073 (14)	C7—H7B	0.9900
O4—C6	1.3347 (15)	C8—H8A	0.9800
O4—C7	1.4611 (14)	C8—H8B	0.9800
O5—C10	1.3599 (15)	C8—H8C	0.9800
O5—H6	0.912 (16)	C9—C14	1.3922 (17)
N1—C4	1.3674 (15)	C9—C10	1.3986 (17)
N1—C1	1.4472 (16)	C10—C11	1.3971 (17)
N1—H4	0.836 (14)	C11—C12	1.3795 (18)
N2—C4	1.3373 (16)	C11—H11	0.9500
N2—C3	1.4606 (15)	C12—C13	1.3886 (19)
N2—H5	0.867 (14)	C12—H12	0.9500
C1—C2	1.5344 (16)	C13—C14	1.3856 (18)
C1—C5	1.5407 (18)	C13—H13	0.9500
C2—C6	1.5254 (16)	C14—H14	0.9500
C1—O1—H1	106.7 (11)	F3—C5—C1	111.93 (10)
C6—O4—C7	116.81 (10)	O3—C6—O4	124.46 (11)
C10—O5—H6	109.5 (10)	O3—C6—C2	125.69 (12)
C4—N1—C1	125.39 (10)	O4—C6—C2	109.59 (10)
C4—N1—H4	113.9 (9)	O4—C7—C8	106.41 (10)
C1—N1—H4	119.4 (9)	O4—C7—H7A	110.4
C4—N2—C3	123.51 (10)	C8—C7—H7A	110.4
C4—N2—H5	117.4 (9)	O4—C7—H7B	110.4
C3—N2—H5	118.2 (9)	C8—C7—H7B	110.4
O1—C1—N1	113.07 (10)	H7A—C7—H7B	108.6
O1—C1—C2	110.26 (10)	C7—C8—H8A	109.5
N1—C1—C2	108.19 (9)	C7—C8—H8B	109.5
O1—C1—C5	108.17 (9)	H8A—C8—H8B	109.5
N1—C1—C5	107.50 (10)	C7—C8—H8C	109.5
C2—C1—C5	109.58 (10)	H8A—C8—H8C	109.5
C6—C2—C1	117.10 (9)	H8B—C8—H8C	109.5
C6—C2—C3	106.28 (10)	C14—C9—C10	119.03 (11)
C1—C2—C3	109.92 (10)	C14—C9—C3	120.77 (11)
C6—C2—H2	107.7	C10—C9—C3	120.12 (11)
C1—C2—H2	107.7	O5—C10—C11	122.76 (11)
C3—C2—H2	107.7	O5—C10—C9	117.82 (10)
N2—C3—C9	110.95 (9)	C11—C10—C9	119.42 (11)
N2—C3—C2	106.50 (10)	C12—C11—C10	120.64 (12)
C9—C3—C2	110.89 (10)	C12—C11—H11	119.7
N2—C3—H3	109.5	C10—C11—H11	119.7
C9—C3—H3	109.5	C11—C12—C13	120.35 (12)
C2—C3—H3	109.5	C11—C12—H12	119.8
O2—C4—N2	121.47 (11)	C13—C12—H12	119.8
O2—C4—N1	120.20 (11)	C14—C13—C12	119.15 (13)
N2—C4—N1	118.31 (11)	C14—C13—H13	120.4
F2—C5—F1	107.99 (10)	C12—C13—H13	120.4
F2—C5—F3	106.92 (10)	C13—C14—C9	121.39 (12)
F1—C5—F3	107.15 (10)	C13—C14—H14	119.3
F2—C5—C1	111.86 (10)	C9—C14—H14	119.3
F1—C5—C1	110.74 (10)
C4—N1—C1—O1	98.15 (14)	O1—C1—C5—F3	−176.35 (10)
C4—N1—C1—C2	−24.26 (16)	N1—C1—C5—F3	61.24 (13)
C4—N1—C1—C5	−142.52 (11)	C2—C1—C5—F3	−56.12 (13)
O1—C1—C2—C6	49.05 (14)	C7—O4—C6—O3	−13.82 (17)
N1—C1—C2—C6	173.17 (10)	C7—O4—C6—C2	160.62 (10)
C5—C1—C2—C6	−69.90 (13)	C1—C2—C6—O3	−60.93 (16)
O1—C1—C2—C3	−72.30 (12)	C3—C2—C6—O3	62.31 (15)
N1—C1—C2—C3	51.82 (13)	C1—C2—C6—O4	124.72 (11)
C5—C1—C2—C3	168.75 (9)	C3—C2—C6—O4	−112.04 (11)
C4—N2—C3—C9	158.86 (11)	C6—O4—C7—C8	176.95 (10)
C4—N2—C3—C2	38.09 (16)	N2—C3—C9—C14	−51.23 (16)
C6—C2—C3—N2	174.26 (10)	C2—C3—C9—C14	66.90 (14)
C1—C2—C3—N2	−58.11 (12)	N2—C3—C9—C10	132.13 (12)
C6—C2—C3—C9	53.45 (12)	C2—C3—C9—C10	−109.73 (13)
C1—C2—C3—C9	−178.92 (9)	C14—C9—C10—O5	−177.92 (11)
C3—N2—C4—O2	171.65 (11)	C3—C9—C10—O5	−1.22 (17)
C3—N2—C4—N1	−10.02 (18)	C14—C9—C10—C11	1.67 (18)
C1—N1—C4—O2	−179.52 (11)	C3—C9—C10—C11	178.36 (11)
C1—N1—C4—N2	2.12 (18)	O5—C10—C11—C12	178.89 (12)
O1—C1—C5—F2	63.67 (12)	C9—C10—C11—C12	−0.68 (19)
N1—C1—C5—F2	−58.74 (13)	C10—C11—C12—C13	−0.5 (2)
C2—C1—C5—F2	−176.10 (9)	C11—C12—C13—C14	0.7 (2)
O1—C1—C5—F1	−56.85 (13)	C12—C13—C14—C9	0.3 (2)
N1—C1—C5—F1	−179.26 (10)	C10—C9—C14—C13	−1.49 (19)
C2—C1—C5—F1	63.38 (12)	C3—C9—C14—C13	−178.16 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O1i	0.836 (14)	2.244 (14)	3.0760 (13)	174.1 (14)
N2—H5···O2ii	0.867 (14)	2.040 (15)	2.9064 (14)	177.4 (13)
O1—H1···O5i	0.858 (17)	2.588 (16)	3.0983 (13)	119.2 (13)
O1—H1···O3i	0.858 (17)	2.013 (17)	2.8232 (13)	157.1 (15)
O5—H6···O2iii	0.912 (16)	1.759 (17)	2.6685 (12)	175.8 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H4⋯O1i	0.836 (14)	2.244 (14)	3.0760 (13)	174.1 (14)
N2—H5⋯O2ii	0.867 (14)	2.040 (15)	2.9064 (14)	177.4 (13)
O1—H1⋯O5i	0.858 (17)	2.588 (16)	3.0983 (13)	119.2 (13)
O1—H1⋯O3i	0.858 (17)	2.013 (17)	2.8232 (13)	157.1 (15)
O5—H6⋯O2iii	0.912 (16)	1.759 (17)	2.6685 (12)	175.8 (14)

Symmetry codes: (i) ; (ii) ; (iii) .